Process for dehydrogenating hydrocarbons using as catalyst calcium oxide on calcium carbonate



co, Aboeo June 29,1948.

B. B. coRsoN E1 AL PROCESS FOR DEHYDROGENATING HYDROCARBONS USING AS CATALYST CALCIUM OXIDE 0N CALCIUM CARBONATE Filed Dec. 31, 1943 CO2 ADDE D ZOFF -co OFF OPE RAT 5 3 v u Q SSVd aad anaaus'o; OELZBANOD- anaznaeuma 4N2; aad .mplam ING TIME. IN H 025 GO OPERATING TIME IN HOURS a l l K Jew Aemvzrr Cbmu, and Game My rlmqwjaa.

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Patented June 29, 1948 PROCESS FOR DEHYDROGENATING I IY- DROCARBONS USING AS CATALYST CAL- CIUM OXIDE ON CALCIUM CARBONATE Ben Bennett Corson and George Arthur Webb,

Pittsburgh, Pa., assignors, by mesne assignments, to Koppers Company, Inc., a corpora tion of Delaware Application December 31,'1943, Serial No. 516,352

14 Claims.

1 The present invention relates in general to dehydrogenation catalysts and comprehends improvements in catalysts adapted more especially to the dehydrogenation of aliphatics and particularly to the dehydrogenation of the aliphatic side-chains of alkylaromatics having a plurality of carbon atoms in said side chains; for example, the conversion of isobutane to isobutylene and of ethylbenzenes into styrenes.

An object of the present invention is the provision of improved and less expensive forms of the known catalysts of lime, magnesia, and mixtures thereof for example with, or without, iron oxide for carrying on reactions belongin to the above-stated classes.

A further object of improvement is to provide for the present uses easily available natural minerals and other naturally-occurring products that are easily convertible either by pretreatment, or automatically in use, to catalysts for the stated purposes.

A further object of invention is to provide improvements both for the preparation and subsequent operation of catalysts of the stated types whereby their physical integrity and effective activity can be assured over importantly prolonged operating periods.

The invention has for further objects such other improvements and such other operative advantages or results as may be found to obtain in the processes or apparatus hereinafter described or claimed.

It is known that both lime and magnesia, either individually or in admixture, or containing a fractional proportion of iron oxides, provide good catalysts for dehydrogenation reactions involving especially the aliphatic side-chains of alkylaromatics. The lime and magnesia as usually prepared are either pulverulent or, structurally, highly friable lumps, and their successful use has heretofore necessitated, in order to provide them with the required resistance to crushing and packing demanded in large-scale operations, that these materials be formed into pellets or be supported on structurally sturdy carriers such as active carbon, silica gel, Florida earth, or the like, which also provide the large surface areas whereby said compounds are brought into intimate contact with the aliphatic or alkylaromatic compounds to be dehydrogenated. n

It has now been found by the present co-inventors that particularly desirable and rugged forms of lime and magnesia with or without appropriate contents, for example, of iron oxide can be easily prepared by the calcination at suitable temperatures of superficial portions only of granules of such natural products as marble, limestone, dolomite, dolomitic limestone, and the like, as well as certain other natural modifications of said substances containing iron oxide, as will be hereinafter named and particularized. By so performing the calcination of the granular said materials that the required evolution of carbon dioxide is restricted substantially completely to the outer portions of the granules, the high resistance to crushing and the sturdy structure naturally inherent to the limestone, dolomite, et cetera, can be in greater part preserved in the interior cores of the granules and their outer portions will comprise, to a depth determined by the extent of calcination, a coating of the" required catalytic oxide, or oxides, that is adequately held and supported without other means by the material of the cores themselves, thus providing, relatively simply and cheaply, granules of the required catalytic material having sufficient structural strength that they can be used in beds of considerable depth and for relatively prolonged pci riods without substantial deterioration. Advantageously also, if the oxide-coatings of the soprepared granules are gradually removed from their supporting cores during prolonged operation as may result, for example, from erosion of the vapors of the reaction mixture flowing thereover, it is possible, according to expedients and proce dures that will be hereinafter described, even without removing the granules from the dehydrogenation reactor, to form new quantities of coatings of the oxides on the said granular'cores by further calcination-conversion of-the material minor amount of added carbon dioxide, at eithersubatmospheric, atmospheric, or super-atmospheric pressures, through a reaction zone containing catalytic granules comprising, each a structurally resistant core of the carbonate of calcium, or of magnesium, or mixtures of said carbonates containing or not-containing iron oxide, and an outer layer of an oxide or mixture of oxides of said metals, that is preferably structuraliy integral with said core, such a product,

resulting, for example, from the heating of a granule of such naturally occurring rocks as limestone, dolomite, dolomitlc limestone, and fermginous limestone. These stony materials may also contain, for example, minor proportions of alumina and silica, or other oxides, without important loss of utility for the present purpose; it is, however, undesirable to have any important proportion of their calcium, magnesium, or iron contents in such combination with said alumina,-

silica, or any other compound, that their oxides are not freely liberated and remain in that form during the calcination and subsequent cooling of said stony materials. A simple criterion of the appropriateness of a said natural rock for the present purpose is 1 percentage loss by weight upon complete igniti n which is indicative of the amount of the oxides of calcium, magnesium, or iron that can be liberated from their carbonates by the calcination step. Good results have been obtained with carbonate rocks that showed a loss of as little as about 21% by weight upon complete ignition, even though their ultimate analyses showed them to contain as much as about 36% by weight of silica. Better yields and conversions to said dehydrogenated organic products have, however, been obtained. in the practice, by

catalytically employing granules, as above-de scribed, that resulted from the superficial calcination ofcthose said stony materials which, upon calcination to constant weight (total possible loss upon ignition), showed a loss of from about 30% to 45% by weight.

In the preparation of the catalytic granules of invention, by calcination of natural rocks containing carbonates of lime, magnesia, and the like, the temperature of calcination is or considerable import, the calcination being preferably carried out within the temperature range of about GOT-650 C. instead of the 900 C., or above, temperatures usually employed in the art when said rocks are calcined for their complete conversion to lime, magnesia, or mixtures thereof.

The thickness of the layer of said metallic oxide, or oxides, supported on the carbonate core of the catalyst granules depends, amongst other factors, upon the temperature of calcination and upon the length of time the raw rock granules are treated at said temperature. For the present dehydrogenation reaction, a good catalytic surface condition has been produced in granules of a specific dolomite by calcining the granules at 650 C. for three hours. In the case of a dolomite from another source the best producible catalytic surface condition had not been produced even after twelve hours of calcination at 650 C.

The duration of the calcination step to achieve the optimum catalytic surface condition for the purpose should be determined empirically for the specific raw rock to be employed. It can in general be said, however, that when the calcination step is performed outside the dehydrogenation reactor apparatus, and consequently in the absence of any materials undergoing dehydrogenation, as for example in any heated zone capable of maintaining the rock granules in the stated 600 to 650 C. range of temperatures'and of permitting free exit of the evolved gases therefrom, a satisfactory catalyst product can be ordinarily produced in between three to twelve hours in the case of raw carbonate-rock granules that pass through and are retained on, respectively, screens of four and ten mesh. In the cases of dolomites, limestones, and the like, containing also iron oxide, or carbonate of iron, the calcination period can be reduced below that which would otherwise obtain, because the presence of iron assists in thedecomposition of calcium and of magnesium carbonates into their oxides and carbon dioxide.

As above indicated, the raw carbonate-rock granules can be converted to the catalyst of invention in the above-prescribed manner before they are installed in the dehydrogenation reactor and before the organic compounds to be dehydrogenated are brought into contact therewith. In other words, the raw carbonate-rock granules can be activated by a precalcination" step.

The preparation of the instant novel catalyst products is, however, not limited to such ".preealcination step, because substantially the same said products and reactivities thereof can be achieved by surficial calcination of the raw carbonate-rockgranules in situ" in the dehydrogenation reactor by merely flowing thereover I left as calcination-residuum of said carbonates,

are highly effective for the purpose, in those instances, where the raw carbonate-rock granules are catalytically activated in situ" in the dehydrogenation reactor, it will be found that the full activity 'of the so-formed catalyst product is not achieved immediately but is progressively attained after a relativelyextended induction period. If the activation of the raw-carbonate rock is accomplished by flowing thereover at about 650 C. a mixture of some steam and vapors of the organic compound to be dehydrogenated it will be observed, during the initial period of passing of such vaporous mixture, that little or no dehydrogenation of the employed organic compound will be effected. With continued passage,

-however, of said vaporous mixture, the dehydrogenation ofa relatively minor proportion of the so-passed 0..1'Zanic compound will be detected in reaction-products issuing from contact with the carbonate-rock; this 'indicates that a small amount of the metallic oxide, or oxides, has been formed on-the surface thereof. with further continued passage of said vaporous mixture, the formation of more and more of the oxides is indicated by increasing content of dehydrogenation product of the organic compound in said reactionproducts. with continued increase of oxidei'ormation on the surface of the carbonate-rock, there. will ultimately be reached a stage where. if the proportion of employed steam is inadequate, the produced oxide-surface becomes so active that the deposition thereon of carbon, re-

' metallic carbonate.

' ever, that if the proportion of steam in themixture thereof with the to-be-dehydrogenated organic compound introduced into the dehydrowater-gas reaction), the catalytic oxide-coatings of the carbonate-rock granules can be maintained effectively free of said carbon and their activity will continue for protracted periods to remain unimpaired for dehydrogenation purposes.

The effective life of the present catalytic-material does not, however, depend merely on providing oxide-coatings for the carbonate-rock granules, or on maintaining said coatings during operation substantially free of deposited carbon, for the reason that the carbonate cores, upon which the catalytic material depends for its continued structural integrity, exhibit in the reaction zone, within the eifectivetemperature-range of dehydrogenation, a positive partial pressure of carbon dioxide which can lead to the more or less rapid disintegration of the carbonate core and consequent loss of utility of the catalyst material.

The present improvement therefore further provides, when employing the catalysts of invention, for observance and regulation of the carbondioxide partial pressure in the zone of dehydrogenation during divers periods of a cycle of operation. In those instances, where the oxide coatings are formed on the rock-carbonate granules in situ" in the dehydrogenation reactor, as above described, the rate or flow of vapor thereover must be sufilciently rapid, during the induction or oxide-forming stage, to maintain the partial pressure of carbon dioxide in the reactor atmosphere below at most the decomposition pressure of the carbon dioxide evolved from the employed rock-carbonate granules at the existing reactor temperature; otherwise, there will be no oxide formation and the catalyst product will not develop. During this said induction stage there should also be at all times sumcient proportion of steam in the said flowing mixture of reactants both to form water-gas with any carbon incidentally deposited on the metallic oxide coatings undergoing formation and also to remove, from the reactor, any so-formed carbon dioxide at a partial pressure less than the carbon-dioxide decomposition pressure of the rock-carbonate; otherwise, any previously formed metallic oxide will be reconverted into the catalytically inactive Ultimately, in the cycle of operation, when sufllcient oi the metallic oxide,

From the above-recited, it obviously lies within the skill of the operator, by appropriate control of the carbon-dioxide partial pressure in the atmosphere in the dehydrogenation reactor, to form therein from the raw carbonate-rock granules the active dehydrogenation catalyst-product of the invention, to retain it in its active form, to preserve its physical structure through protracted cycles of operation, to maintain it eifectively free of carbon deposited thereon by incidental, unwanted side-reactions, and also to reduce, it necessary, any excessive reactivity thereof. 1

Manifestly, in those instances where rockcarbonate granules areprecalcined" outside the dehydrogenation reactor to their wanted activity, it only remains for the operator to provide, .in the admixture of steam and organic compound introduced into the reactor, that quantity of the former component which prevents effective deposition of pyrolytic carbon on the catalyst surfaces and also gives a partial pressure of carbon dioxide in the reactor atmosphere that is at least substantially equal to the decomposition pressure of the rock-carbonate in respect of said gas.

The partial pressure of carbon dioxide that should be maintained in the reactor atmosphere at various stages in the above-described operating cycle will vary from application to application and also with the nature of the raw carbonate-rock employed, as is indicated by the following table showing the carbon-dioxide partial pressure, at the dehydrogenation temperature of 650 C., of some natural products that are useful for the present application:

Ferruginous Dolomite Magnesia, as well as that natural mixture of lime, magnesia, and iron oxide formed by the calcination of certain ferruginous dolomites, provide especially reactive dehydrogenation cataor oxides, has been formed on the surface of said 1 granules to produce an eflective catalytic-coating thereof, the partial pressure of carbon dioxide in the reactor atmosphere, in the interest of preserving the rock-carbonate cores of the catalyst granules and consequently their rugged structure, must be increased, for example by decreasing the steam component of the catalytically treated mixoperating periods.

lysts. However, the raw rock-carbonates from which they are formed, as shown above, have relatively high partial pressures of carbon dioxide at 650 C. andin the practice it has been found that catalyst-supporting cores of such materials when employing the most practical ratio of steam to organic-compound vapors introduced in the dehydrogenation reactor, are not as easily retained in a structurally stable condition as obtains in the case of the dolomite and limestone cores. This is principally in consequence of the fact that the carbon incidentally deposited, as aforesaid, on the catalyst-surface during operation is insumcient when removed therefrom by means of the water-gas reaction to provide adequate partial pressureof carbon dioxide in the reactor atmosphere completely to prevent substantial decomposition of the magnesite and certain ferruginous dolomite cores during protracted In their cases, ithas been found advantageous to add to reactants passing to the reactor, carbon dioxide from an outside source, for example combustion-products, in quantity suflicient to provide in addition to that carbon dioxide which is formed by the said lowtemperature water-gas reaction, a carbon-dioxide partial pressure in the reactor atmosphere that is at least about the decomposition pressure of carbon dioxide of said carbonate materials.

ing forming a part of this specification, there is graphically shown the operative eflects that can be obtained by careful observance and control of the carbon-dioxide partial pressure of the reactor-atmosphere when employing an improved catalyst of invention. The single curve of said figure represents the operating effects and results obtained in the employment of a said catalyst that was prepared from dolomite granules of sizes of 4 to 10 mesh. These granules were partially activated by their heating for three hours at about 650 C. after which they were charged into the dehydrogenation reactor, with their soproduced surficial coatings of a mixture of lime and magnesia. Their complete activation was effected fin situ" in said reactor by flowing thereover at a temperature of about 650 C. a preheated stream of mixed steam and vaporous ethylbenzene in the respective ratio by volume of approximately 10:1 while employing a contact time of 0.9 second. Hours of operation are plotted in said figure as abscissae and the percentage conversion, by weight, of ethylbenzene per pass over the heated catalyst is plotted as ordinates.

From an initial conversion to styrene of about 26% by weight of the ethylbenzene brought into contact with the dolomite granules that had been merely precalcined for three hours, the conversion ofethylbenzene to said product increased,

after about eighteen hours of the described operatlon, to about 37%, per pass over the catalyst, and continued at this conversion level for the next about forty-seven operating hours. After about the first twenty-five or thirty hours of the described operation, as shown by the curve of Fig. 1, the catalyst had reached substantially its full activity and continued so to function, without diminution, to the sixty-fifth hour. These results show that with the specific dolomite employed, a mere three-hour precalcination period was insuillcient to provide the dolomite granules with their most active thickness of oxide-coating which was later achieved in actual operation. During the said forty-seven-hour operating period, there was substantially no deposition of carbon accumulated on the catalyst surface and the partial pressure of carbon dioxide in the reactor atmosphere was in substantial equilibrium with the decomposition pressure of the dolomitic cores of the catalyst in respect of carbon dioxide, and the catalyst retained its rugged structure unchanged throughout said operating period. If the above steam-toeethylbenzene ratio had been sufficiently greater than that employed to have diluted the water-gas-derived carbon dioxide to a point where its partial pressure was less than the decomposition pressure of the catalyst cores in respect thereof, the catalyst would have lost its sturdy physical structure and, in a time interval corresponding substantially proportionally catalyst cores in respect thereof, the active limemagnesia coating of said cores would have been more or less rapidly, respectively, either smothered by carbon or have been converted to the catalytically inactive carbonates of lime and magnesia, and in either event the activity of the catalyst would have soon been lost.

Referring again to the curve of Fig. 1, this urgency of controi of the carbon-dioxide partial pressure in the dehydrogenation reactor in the interest of ensuring a long effective life of the catalyst body is forcefully demonstrated. The curve of said figure shows, as above recited, that at the sixty-fifth operating hour and under the stated operating conditions about 37% of'the ethylbenzene passed over the catalyst was converted to styrene and that the process system had been in equilibrium for about 35 operating hours, At the end of the sixty-fifth hour, sufflcient carbon dioxide from an extraneous source was introduced into the ethylbenzene-stream admixture flowing to the dehydrogenatlng reactor to raise the carbon-dioxide partial pressure of the atmosphere therein to about 35 mm. Hg; 1. e., to about twice the decomposition pressure of the dolomite cores of catalyst granules in respect of said carbon dioxide. The eiiiciency of conversion of ethylbenzene to styrene started immediately to decrease and in twelve hours had been reduced to only about 20% by weight of the treated ethylbenzene in consequence of the conversion of the lime-magnesia coatings of the catalyst granules to their inactive carbonates. Thereafter, the extraneous introduction of carbon dioxide was discontinued and the carbondioxide partial pressure in the reactor was decreased, for example, by increasing the proportion of steam in the ethylbenzene-steam mixture employed until the carbon-dioxide partial pressure in the reactor became less than the decomposition pressure of the dolomite in respect of carbon dioxide, and after about forty additional hours of operation, the activity of the catalyst granules had been completely restored to that obtaining before introduction of the extraneous carbon dioxide. The proportion of steam in said admixture was then restored to the 10:1 ratio originally obtaining and the styrene production was maintained for about twenty hours at the originally high level. Thereafter, the described cycle was repeated, as shown in the final portion of the curve, in confirmation of the above.

The accompanying Fig, 2 shows by means of its two curves the distinction in catalytic activity, for the present purpose, between dolomitic limestone granules that had been calcined at a temperature of about 920 C. and the same dolomitic granules that were surficially precalcined to the degreeof such partial-pressure reduction.

would have changed completely, although still active, to a highly friable mixture of lime and magnesia that would rapidly disintegrate and 1 pack and give rise to inoperative resistance to flow of vapors through the reactor. Conversely,

if the proportion of steam in the vaporous mixture introduced into the reactor had beenso low that pyrolytically formed carbon was either inadequately removed from the catalyst surface by the low-temperature water-gas reaction, or, was even so-removed but at a carbon-dioxide partial pressure in the reactor atmosphere somewhat greater than the decomposition pressure of, the

for 12 hours at a temperature of 650 0., the surfaces thereof being further activated and brought to maximum activity in situ" in the dehydrogenation reactor during actual conversion of ethylbenzene to styrene at 650 C. The curve formed by the line A represents the conversion capacity of the dolomite that was calcined at the. higher said temperature whereas the line B shows the activity of the same raw material prepared at the lower said temperature and only surficially calcined. The operating conditions duringboth run periods were maintained substantially the same; i. e., the conversion temperature of ethylbenzene to styrene was 650 C., the steam-ethylbenzene ratio was 10:1, and the contact time was 0.9 second.

Reference to the above curves clearly shows that in the case of dolomite calcined at a temperature of about 920 C., the conversion of ethylbenzene to styrene through seventy hours of said operation never exceeded more than about 22% by weight or ethylbenzene per pass whereas in the case of the same dolomite surficially calcined at 650 C., the said conversion exceeded that of the former material after about fifteen hours of D- eration and increased, at about forty hours to about 32-33% and so continued for the remainder of an operating period of 140 hours when operation was discontinued. I

As hereinbefore mentioned, a wide variety of minerals, rocks, and other natural products containing carbonates of calcium and magnesium are of utility for the present purpose ranging from pure magnesites, dolomites, dolomitic limestones, limestones, marbles, and also these materials containing impurities such as silica, metallic oxides and especially an oxide, or oxides of iron.

When employing substantially the same operating conditions, the by-weight conversion of ethylbenzene to styrene per pass over surficially calcined magneslte and dolomite is higher than is the case with limestone, and the dolomite is preferable to the magnesite because, even though the magnesite is slightly the more selective for the ethylbenzene conversion. it has such a relatively high decomposition pressure in respect 01' carbon dioxide within the range of temperatures wherein it is catalyticallyv active to promote said conversion that extraneous carbon dioxide may need addition to the atmosphere of the dehydrogena tion reactor to prevent complete disintegration of the magnesite cores of tlie catalyst granules if prolonged use of thatc talyst is an important factor. and also because the surflclal coatings of magnesia are less reactive than the lime-mag! nesia coating provided by a dolomite to promote the low-temperature water-gas reaction whereby pyroiyticaliy-formed carbon is inhibited accumulating on the catalysts surfaces. Thus the magnesite coatings are more likely to become coated with carbon than are coatings of a mixture of lime and magnesia.

Ferruginous limestones have been found of special merit for the present purpose. Upon surficiai calcination, they provide a mixture of the oxides of calcium, magnesium, and iron. They can be prepared according to the invention as catalytic granules of such stable structure and crushing strength that they are useful in largescale operations. Representative of this latter class of natural products are those found in deposits located at Clinton, New York, and are obtainabie in the trade as low-grade iron ores. Materials from this source and known in commerce as Red Fluxes Nos 1 and 2 are of especial utility,

the former containing about 30% FezOa and the latter about 12% of the same, the remainder being essentially dolomitic limestone and a minor amount of silica. Under essentially the same operating conditions the surficially calcined No. 2 Red Flux granules gave an average conversion of ethylbenzene to styrene of 48% by weight per pass of a :1 mixture respectively of steam and ethyibenzene thereover at a conversion temperature of 650 C. whereas the Red Flux No. 1 gave an average conversion of slightly less; that is, 42%.

Those surficially calcined granules of limestones, dolomitic limestones, or dolomites that contain essentially no other metallic oxides can be advantageously treated for their increased activity with minor proportions of, for example,

iron oxide, or nickel oxide applied in any expedient manner and preferably in a fashion that will obviate slaking of the surflcial coatings of the oxides or calcium, magnesium, or both; for example, suspensions of said oxides of iron or of nickel in a non-hydrous medium can be sprayed over the said calcined granules. Similarly, it is also feasible for purpose of increasing the resistance to erosion of said surflcial coatings to disperse therein a relatively minor proportion of a salt. or the like, for example a compound of silica,

that functions at the temperature of dehydrogenation to form .a fibrous skeleton of sillcious material therein. i I

The following examples are illustrative of results that have been obtained in the practice of the invention; in said examples, the term "average per cent conversion" indicates the proportion by weight of parafllnic or alkyl aromatic hydroc rbons, in the steam-hydrocarbon mixture, that dehyrogenated by a single contacting with, or passage over, the employed catalyst under the stated operating conditions whereas the "average total yield represents the proportion by weight of dehydrogenated product that is producible from a given quantity or the material to be dehydrogenated by repeatedly returning to contact with the catalyst any undehydrogenated portion of said quantity. The examples follow:

Example No. 1

Minus four to plus 10 mesh granules of a limestone containing about 6% oi. silica, 1.2% of FezOa, the remainder being essentially CaCOa, were heated at about 650 C. for about three hours in apparatus permitting free evolution of carbon dioxide, thereby providing on said granules a surflcial coating consisting essentially of calcium oxide. Over the so-prepared granular catalyst in reactor apparatus a steam-ethylbenzene mixture containing said components in the ratio of 10: 1 by volume was continuously flowed at a temperature of about 650 C. for 90 hours. The average per cent conversion of the treated ethylbenzene to styrene was 36% and the average total yield was 78% by weight, at a contact time 01' 0.9 second for said mixture. At the end of said 90- hour operating period,'the limestone cores of said granular catalyst constituted nearly 60% by weight or the granular catalyst which was still highly efl'ective for the purpose when operation was discontinued. The cooled catalyst contained as a carbon deposit 0.06% by weight of the treated 'ethylbenzene, and over 90% of the elemental carbonliberated in the reactor apparatus by Pyrolytic reaction. was continuously removed as carbon dioxide in the eliluent vapors.

Example No. 2

A sample of marble chips of mesh sizes minus 4 and plus 10 were heated to 650 C. for three hours while passing thereover steam preheated to said temperature. Thereafter, a steam-ethylbenzene mix-ture was continuously flowed thereover at a contact time of 0.92 second and at a temperature of 650 C. for 5 days. The average conversion of ethylbenzene to styrene was 35% and the average total yield of styrene was by weight or treated ethylbenzene. At the end of said 5 days of operation, the marble cores of said catalyst constituted about 55% by weight thereof. About 0.25% by weight of the treated ethylbenzene was present as unremoved carbon in the cooled catatlyst; about of the tormed elemental car- 11 'bon was continuously removed from the reactor in the efllu'ent vapors.

Example No. 3

Raw granules of Red Flux No. 2, hereinabove. referred to and its origin described, and containing about 5% $102, 12.5% of F8203, 47% CaCOa. 31%, MgCOa, and a small amount of A1203, were introduced into a reactor vessel without any preheating or calcining. A vaporous mixture of steam and ethylbenzene in the ratio by volume of 10:1 was preheated to about 650 C. and immediately flowed into contact with the said granules of Red Flux in said reactor. A stream of the said preheated admixture was continuously flowed Example No. 4

A granulated dolomitic limestone containing about 11.5% of SiOz, 4.6% A1203, 12% FeCOs, 42% CaCOa and 28% MgCOa was screened and the minus 4.and plus 10 mesh sizes were in admixture precaicined at about 650 C. for three hours under conditions permitting free escape of the evolved gas. In the said limestone, the magnesium and calcium carbonates were in the mole ratio of substantially 121.3. A vaporous stream that was a mixture of steam and ethylbenzene in the ratio of 10:1 and at a temperature of 650 C. was then continuously flowed over the said precalcined dolomitic granules for a period of 2.75 days. The contact time of said mixture with the surficially calcined said limestone was maintained at 0.92 second. During this entire period an average of 41% by weight of the ethylbenzene in said stream was converted to styrene and by recycling of the unconverted ethylbenzene into contact with the catalyst 71% of a given quantity of ethylbenzene was converted to styrene. The catalyst was still operative to produce styrene at the stated rate when the run was interrupted.

Example No. 5

A vaporous admixture of steam and diethylbenzene in the volume ratio of 10:1 and at a contact time of 0.8 second was flowed at a temperature of 650 C. over dolomitic limestone granules (minus 4 to plus 10 mesh) that had been surflcially precalcined'at a temperature of about 650 C. for about 3 hours. From 240 parts by weight of sotreated diethylbenzene there was obtained 70% by weight of liquid products which contained 52.2%, 19.7%, and 9.9% by weight respectively of diethylbenzene, styrene, and divinylbenzene. Recycling of the undehydrogenated diethylbenzene into contact with the catalyst gave as a total yield from a given Weight of said compound, 21% of divinylbenzene and 41% of styrene, by weight.

Example N0. 6

Isopropylbenzene in vapor form diluted with 9 volumes of steam was flowed at 0.9 second contact time over dolomite granules surficially precalcined at 650 C., at a contact time 05 0.9 second and at an hourly liquid space velocity of 0.4 and at a temperature of 650 C. From 648 parts by wei ht of so-treated isopropylbenzene there were obtained 572 parts by weight of condensed liquid products which contained 32.5%, 13.2%, and 31.0% respectively of isopropylbenzene, styrene, and a-methylstyrene. Recycling of the unconverted isopropyibenzene to the dehydrogenation zone gave a yield of 46% by weight of methylstyrene from a given quantity of isopropylbenzene,

Example No. 7

Granular dolomite ,of minus four to plus ten mesh was calcined for 3 hours at 650 C. Over the so-treated dolomite at a temperature of 650 C. and at a contact time of 1.0 second a mixture of steam and mono-ethylnaphthalene in the molar ratio of 10:1 was continuously flowed for an opcrating period of hours. During this time the average per cent conversion of the ethylnaphthalene to vinylnaphthalene was 36.4% by weight. The average total yield was 70.3% by weight of the latter said compound. There was also produced about 3.7% and-4.8% by weight respectively of naphthalene and methyl-naphthalene along with about 2.8% by weight of a gaseous mixture comprising by volume about 92% hydrogen and minor amounts of ethylene and parafiinic compounds. 91% of the elemental carbon liberated in the reactor apparatus was continuously removed therefrom as carbon dioxide in the elliuent vapors.

Example No. 8

Granular dolomite was partially calcined by heating the same several hours at 650 C., in the presence of an inert gas. A mixture of isobutane and water vapor in molar ratio of 1:5 was then flowed over said calcined granules in reactor apparatus while maintaining their temperature at 650 C.. the contact time of said mixture with said granules being 0.4 second. Substantially 20% of the so-treated isobutane was continuously dehydrogenated, about 55% by weight of the so-converted isobutane being isobutylene and the remainder being propylene. Under substantially the same operating conditions but in the absence of water vapor, substantially 20% of the treated isobutane was also dehydrogenated, about 48% by weight being isobutylene and the remainder propylene. In the latter case, however, the activity of the novel catalyst was rapidly lost due to deposition of carbon thereon accompanied by deterioration of its structure. W

The present co-inventors, as above set forth, provide important improvementsin the art of manufacturing and employing dehydrogenation catalysts. The novel catalysts are conveniently and cheaply preparable directly from easily obtainable source materials. They have an improved activity and inherently such rugged structure that they are directly usable in large scale operation without special and expensive preparation, such as pilling and the like, to increase their mechanical strength, Methods of operation are provided whereby this mechanical strength and improved activity can be easily and simply retained in protracted, uninterrupted operation and whereby that usual carbonization of catalysts belonging to the same class. which renders them rapidly inactive, can be eflfectively impeded.

Those features of invention exemplified in the foregoing description which relate to the dehydrogenation catalyst per se, and method of preparing the same, are made the subject matter oi our nonendin application for Letters Patent or 13 the United States, filed September 25, 1947, Serial No. 776,130.

The invention as hereinabove set forth is embodied in particular form and manner but may be variously embodied within the scope of the claims hereinafter made.

We claim 1. An improved method of dehydrogenating a hydrocarbon, said process comprising the steps oi: in the presence of water vapor bringing vapor of said hydrocarbon into contact with a catalyst'that is at a dehydrogenating temperature and comprises an oxid chosen from the group consisting of calcium oxide and magnesium oxide supported on carrier means containing a carbonate of the chosen metal that exerts a partial pressure of carbon dioxide at said dehydrogenating temperature and thereby dehydrogenating said hydrocarbon and also forming carbon dioxide by reaction of water vapor with carbon that is fortuitously liberated from a portion or the said hydrocarbon vapor during said dehydrogenation, and maintaining the partial pressure of carbon dioxide in the atmosphere of said catalyst in substan-' tial equilibrium with the carbon dioxide partial pressure of said carbonate of said carrier means by means including regulating the proportionate ratio of water vapor to hydrocarbon vapor in the atmosphere of the catalyst,

2. A catalytic process for catalytically dehy-- 1 drogenating a hydrocarbon which comprises: subjecting the hydrocarbon reactant to reaction conditions for dehydrogenation thereof under operatin conditions requiring special structural formation of the catalyst particles to providethem with the sturdy physical structure required for resistance to crushing and packing to avoid inoperative resistance to fiow of vapors through the catalyst particles at a temperature between 600- 650 C., in the presence of a catalyst comprising partially calcined granules of particles chosen from the group consisting of carbonate of magnesium and carbonate of calcium, and comprising a maior portion of carbonate and a minor portion of oxide, in which the minor portion by weight of the granules is in the form of decarbonated surflcial outer portions integral with core-like, inner portions and is the catalytically active oxidic residuum resulting from so performing the calcination at a temperature between GOO-650 C. that the required evolution of carbon X dioxide is restricted substantially completely to the surficial outer portions, and in which the major portion by weight of the granules is in the form of core-like inner portions of the undecarbonated carbonate product. having preserved therein the high resistance to crushing and sturdy structure naturally inherent to the carbonate product of the particles and structurally supporting the surficial minor outer portions in their weaker structural form as catalytically active oxidic residuum as a result of the evolution of carbon dioxide therefrom during their calcination, and maintaining the said major portion by weight of the catalyst particles in the form of carbonate throughout the dehydrogenation reaction.

3. A catalytic process for the dehydrogenation of a hydrocarbon which comprises: subjecting the hydrocarbon reactant to reaction conditions for dehydrogenation thereof in the presence of a catalyst comprising-calcined granules of particles chosen from the group consisting of carbonate of calcium and carbonate of magnesium, and comprising a major portion of carbonate and a minor portion-of oxide, in which the minor portion by weight of thegranules is in the Iorm of decarbonated surficial outer portions integral with core-like inner portions and is the catalytically active oxidic residuum resulting from so performing the calcination that the required evolution of carbon dioxide is restricted substantially completely to the 'surflcial outer portions.

and in which the major portion by weight of the granules is in the form of core-like inner portions of the undecarbonated carbonate product having preserved therein the high resistance to crushing and sturdy structure naturally inherent to the carbonate of the particles and structurally supporting the surficial minor outer portions in their weaker structural form as catalytically active ox- ,idic residuum as a result of the evolution of car bon dioxide therefrom duringtheir calcination; and regulating the rate of flow of steam over the catalyst to maintain the carbon dioxide partial pressure during the reaction of the hydrocarbon reactant in substantial equilibrium with decomposition pressure with respect to carbon dioxide of the said carbonate compound core-like inner portions, while removing liberated elemental carbon by reaction with the water vapor, to preserve the;core-like inner supporting portions as carbonate and also inhibit quenching of the catalytically active surficial portion by the liberated carbon and also avoiding its conversion into the inactive carbonate form.

4. A process as claimed in claim 2 and in which the reaction comprises the dehydrogenation of ethylbenzene to styrene.

5. A process as claimed in claim 3 and in which the partially calcined granules are regenerated in situ by, periodically temporarily increasing the rate of flow of steam thereover and thereby decreasing the partial pressure of carbon dioxide to less than the partial pressure of the carbonate compound core-like inner portions until new surficial outer minor oxidic portions as aforesaid are formed closer to the center of the granules, leaving new inner major carbonate core-like portions as aforesaid, whereupon the rate of flow of steam is decreased and the carbon dioxide partial pressure again increased to substantial equilibrium with that of the new residual major carbonate core-like inner portions.

6. A process as claimed in claim 2 and in which thepartially calcined granules are granules that have been calcined from particles which on calcination to a constant weight would show a loss of from 30 to 45% by weight.

7. A catalytic process for the dehydrogenation of a hydrocarbon which comprises: subjecting the hydrocarbon reactant to reaction conditions for dehydrogenation thereof in the presence of a catalyst comprising a supporting carrier portion of carbonate of at least one of the group consisting of calcium and magnesium, and a catalytic oxide of at least one of the group consisting of calcium and magnesium, and regulating the rate of flow of steam over the catalyst to maintain the carbon dioxide partial pressure during the reaction of the hydrocarbon reactant in substantial equilibrium with the decomposition pressure with respect to carbon dioxide of the said carbonate supporting carrier portion, while removing liberated elemental carbon by reaction with the water vapor, to preserve the carbonate form of the supporting carrier portion as carbonate and also inhibit quenching of the catalytically active oxidic portion by the liberated carbon and also avoiding its conversion into the inactive carbonate form. 1

magnesium comprise the natural product magnesite.

11. A process as claimed in claim 1, and in which the carbonate chosen from the group consisting-of carbonate of calcium and carbonate of magnesium comprise the natural product dolomite. 1

12. A process as claimed in claim 1, and in which the carbonate chosen from the group consisting of carbonate of calcium and carbonate of magnesium comprise the natural product ferruginouslimestone.

13. A process as claimed in claim 1. and in which the carbonate chosen from the group consisting'oi' carbonate or calcium and carbonate of magnesium comprise the natural product magnesite.

14. A catalytic process for dehydrogenating a hydrocarbon which comprises: subjecting the hydrocarbon reactant to dehydrogenation conditions in the presence of a catalyst and of a conveying current of steam for said hydrocarbon,

said catalyst comprising granules having a core chosen from the group consisting of carbonate of calcium and carbonate magnesium, and having an outer coating of the corresponding'synthetlc oxide and synthetic carbonate supported on the core of the carbonate chosen from said group. regulating the relative rates of steam and hydrocarbon flowed over the catalyst to maintain the partial pressure of carbon dioxide in the atmosphere'of said catalyst in substantial equiiibrium with the carbon-dioxide decomposition pressure 01 said supporting carbonate at the employed operating temperature, and thereby also removing liberated carbon from the catalyst by reaction with said steam, so as to inhibit quenching of the active oxidic portion of the catalyst by deposition of liberated. carbon thereon and to preserve in the form of carbonate the said supporting carrier of said oxidic oxide portion of the catalyst. 1

BEN BENNETT CORSON.

GEORGE ARTHUR WEBB.

' mzraaancns crran' The followingreferences are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,732,381 Schmidt et a] Oct. 22, 1929 1,926,587 Hansgirg Sept. 12. 1933 2,057,402 Tropsch Oct. 13, 1936 2,110,833 Mark et al., Mar, 8, 1938' 2,122,787 Tropsch July 5, 1938 2,194,335 Tropsch Mar. 19, 1940 2,217,009 Grosse et al. Oct. 8, 1940 2,257,082 Yamall Sept. 23, 1941 2,343,295 Bailie et al. Mar. 7, 1944 2,395,875 Kearby a Mar. 5, 1946 2,397,218 Sturgeon Mar. 26, 1946 FOREIGN PATENTS Number Country Date 819,701 France July 12, 1937 OTHER REFERENCES Mellor: Comprehensive Treatise on Inorganic and Theoretical Chemistry, Longmans, Green a 00., 1932. Copy in Div. 59, vol. 3, page 657, vol. 4, pages 352-353. v 

